JPH101822A - Halogen-containing fiber and flame-retardant fiber composite material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a halogen-containing fiber useful for a working wear for fire fighting, excellent in handle, water absorption properties and touch, by adding a specific amount of a zinc stannate compound to a polymer containing a prescribed amount of a halogen. SOLUTION: This halogen-containing fiber is obtained by adding 20-50wt.% of a zinc stannate compound such as zinc stannate or zinc hydroxystannate to a polymer which contains 17-70wt.% of a halogen and comprises 30-70 pts.wt. of acrylonitrile, 70-30 pts.wt. of a halogen containing vinylidene monomer and/or a halogen-containing vinylidene monomer and 0-10 pts.wt. of a vinyl-based monomer copolymerizable with these monomers. The halogen-containing fiber in an amount of 85-15wt.% is combined with 15-85wt.% of a fiber composed of natural fiber and/or a chemical fiber to give the objective flame retardant fiber composite material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a halogen-containing fiber which is highly flame-retarded with a flame retardant, and which is a composite of this halogen-containing fiber and other fibers, which has excellent texture and hygroscopicity,
The present invention relates to a fiber composite having flame retardancy.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for ensuring the safety of clothing, food and shelter. Flame retardancy is strongly demanded not only for interior materials but also for clothing and textiles for bedding as in the past. Demands for feeling, texture, hygroscopicity, washing resistance, durability, and the like are also increasing. Many studies on flame retardancy of fibers have been conducted on specific fibers such as modacrylic fiber, polyclar fiber, polyester fiber, viscose rayon, etc. Have been obtained. However, the fact is that the diversified and sophisticated demands of consumers as described above have not been sufficiently met.

In order to meet such a demand, for example, as disclosed in Japanese Patent Application Laid-Open No. 61-89339, a highly flame-retarded fiber obtained by adding a large amount of a flame retardant and another non-flame-retarded fiber. Research has been conducted to obtain a composite flame-retardant fiber that has the original characteristics of non-flame-retardant fiber by combining fibers, and has an excellent texture as clothing such as cotton and rayon.
By forming a composite fiber obtained by mixing a fiber having a moisture absorbing property and a tactile sensation with a highly flame-retardant fiber, a conjugate fiber having improved texture, moisture absorptivity, and tactile sensation has been developed.

[0004] However, antimony compounds conventionally used as a flame retardant in the above-described composite flame retardant fibers include:
If the amount is increased to some extent, it will be difficult to improve the flame retardancy to match the amount of the antimony compound added, and it cannot be used in fields that require even higher flame retardancy, such as forest security and firefighting work clothes. Was.

[0005]

Accordingly, the present invention has been made in view of the above-mentioned points, and has an extremely high level of flame retardancy while having an excellent texture, moisture absorption and tactile sensation, which is impossible with conventional conjugate fibers. It is an object of the present invention to obtain a flame-retardant fiber composite that can be used in a field that requires a flame retardant.

[0006]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a halogen-containing fiber to which a zinc stannate compound is added in a large amount as a flame retardant has been obtained.
When the amount of the flame retardant is more than a certain amount, compared with the halogen-containing fiber to which a large amount of an antimony compound is added as a flame retardant, it is combined with another fiber such as a natural fiber or a chemical fiber to form a fiber composite. In this case, it was found that the composition exhibited higher flame retardancy, and the present invention was completed.

That is, according to the present invention, a halogen is used in an amount of 17-70.
A halogen-containing fiber comprising a polymer containing 20% to 50% by weight of a zinc stannate compound based on the polymer;
And a flame-retardant fiber composite in which 85 to 15% by weight of the halogen-containing fiber is combined with 15 to 85% by weight of a fiber made of natural fiber and / or chemical fiber.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The halogen-containing fiber comprising the halogen-containing polymer of the present invention contains 17 to 70% by weight, preferably 23 to 44% by weight of halogen. Examples of the fiber containing 17 to 70% by weight of the halogen include a fiber made of a polymer of a monomer containing a halogen and a copolymer of a monomer containing the halogen and a monomer not containing a halogen. Fiber, a polymer blend of a halogen-containing polymer and a halogen-free polymer, or a fiber comprising a halogen-containing polymer into which halogen is introduced by post-processing, and the like. Absent.

Specific examples of the polymer having a halogen include homopolymers or copolymers of halogen-containing monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide, and acrylonitrile. -Vinyl chloride, acrylonitrile-vinylidene chloride, acrylonitrile-vinyl bromide, acrylonitrile-vinyl chloride-vinylidene chloride, acrylonitrile-vinyl chloride-
One or more halogen-containing monomers such as copolymers of halogen-containing monomers such as vinyl bromide, acrylonitrile-vinylidene chloride-vinyl bromide and acrylonitrile, vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide. And acrylonitrile and a copolymer of a vinyl monomer copolymerizable therewith, or a polymer obtained by reacting a halogen-containing compound with an acrylonitrile homopolymer, a halogen-containing polyester, and the like, but are not limited thereto. Not something.

The copolymerizable vinyl monomers include, for example, acrylic acid, esters thereof, methacrylic acid, esters thereof, acrylamide, methacrylamide, vinyl acetate, vinylsulfonic acid, salts thereof, methacrylsulfonic acid, salts thereof , Styrene sulfonic acid, and salts thereof, and one or more of them can be used.

The halogen-containing polymer includes:
A copolymer comprising 30 to 70 parts by weight of acrylonitrile, 70 to 30 parts by weight of a halogen-containing vinyl monomer and / or a halogen-containing vinylidene monomer, and 0 to 10 parts by weight of a vinyl monomer copolymerizable therewith. Is preferred,
More preferably, 40 to 70 parts by weight of acrylonitrile,
A copolymer comprising 60 to 30 parts by weight of a halogen-containing monomer and 0 to 3 parts by weight of a copolymerizable vinyl monomer is preferred. When the acrylonitrile is less than 30 parts by weight, heat resistance is not sufficient, and when the acrylonitrile exceeds 70 parts by weight, a sufficient effect on flame retardancy cannot be obtained. If the amount of the halogen-containing monomer is less than 30 parts by weight, a sufficient effect on the flame retardancy cannot be obtained, and if the amount of the halogen-containing monomer exceeds 70 parts by weight, the heat resistance is not sufficient.

When the halogen content in the halogen-containing fiber is less than the above range, the flame retardancy of the fiber becomes insufficient, and it becomes difficult to maintain the flame retardancy of the composite as a final product. If the ratio exceeds the above range, properties such as physical properties (strength, heat resistance, etc.), dyeability, and texture of the produced fiber become insufficient, and all are not preferable.

The zinc stannate compound contained in the halogen-containing fiber in an amount of 20 to 50% by weight based on the weight of the polymer includes zinc stannate (ZnSnO ₃ ) and zinc hydroxystannate (ZnSn).
Inorganic zinc stannate compounds such as (OH) ₆ ), each of which may be used alone or in combination. If the zinc stannate compound in the fiber is less than the above range, only the same flame-retardant effect as in the case of using an antimony compound such as antimony trioxide can be obtained, and if it exceeds the above range, the produced fiber Problems such as physical properties (strength and elongation), nozzle clogging, clogging of filter cloth and the like occur in the fiber production process, all of which are not preferred.

Examples of the natural fiber and the chemical fiber which are combined with the halogen-containing fiber include natural fibers such as vegetable fibers such as cotton and hemp, and animal fibers such as wool, camel wool, goat wool and silk. Examples of the chemical fibers include, but are not limited to, regenerated fibers such as viscose rayon fibers and cupra fibers, semi-synthetic fibers such as acetate fibers, and synthetic fibers such as nylon fibers, polyester fibers, and acrylic fibers. Not something.

As a method for producing a flame-retardant fiber composite by combining the above-mentioned halogen-containing fiber with other natural fibers or chemical fibers, the respective fibers are blended in a single fiber state or blended. It may be, or a single fiber may be twisted, and further, after producing a yarn with each fiber,
You may interweave.

It is not clear why the fiber composite of the present invention exhibits higher flame retardancy when mixed with natural fibers or chemical fibers to form a composite as the amount of the zinc stannate compound increases. The antimony compound, which has been conventionally used as a fiber flame retardant, suppresses combustion in the gas phase region, whereas the zinc stannate compound used in the present invention is:
This is probably because both the gas phase and the solid phase have the effect of suppressing combustion.

[0017]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The flame retardancy of the fibers in the examples was measured by the oxygen index (LOI method) as follows. Generally, the flame retardancy of fibers is measured and evaluated in the state of woven or knitted fabrics. However, in woven or knitted fabrics, the difference in flame retardancy occurs depending on the number of twists, thickness, number of threads, etc. This is because the flame retardancy cannot be correctly evaluated.

(Measurement of Flame Retardancy) Take 2 g of cotton mixed at a predetermined ratio, divide it into eight equal parts, make eight twists of about 6 cm, and make them stand upright in the holder of the oxygen index tester. The minimum oxygen concentration required to keep burning 5 cm was measured, and this was defined as the LOI value. The higher the LOI value, the more difficult it is to burn and the higher the flame retardancy.

Example 1 A copolymer consisting of 51.0% by weight of acrylonitrile and 49.0% by weight of vinylidene chloride was added to dimethylformaldehyde at a resin concentration of 30% by weight.
It dissolved so that it might become. To the obtained resin solution, zinc hydroxystannate was added so as to be 30% by weight with respect to the copolymer to prepare a spinning dope. This spinning dope was used at 20 ° C. using a nozzle having a nozzle hole diameter of 0.08 mm and 300 holes.
Extruded in 55% aqueous dimethylformamide,
After raising at a rate of 2.5 m / min, washing with water, drying at 130 ° C. for 8 minutes, stretching at 140 ° C. three times, and further performing a heat treatment at 145 ° C. for 5 minutes, the single fiber fineness of 2 denier was obtained. A halogen-containing fiber was obtained. 60% by weight of this halogen-containing fiber and 40% by weight of cotton were mixed.

Comparative Example 1 The same as Example 1 except that antimony trioxide was added in an amount of 30% by weight to the copolymer of Example 1 instead of 30% by weight of zinc hydroxystannate. A halogen-containing fiber added with antimony trioxide was obtained by the method. 60% by weight of this halogen-containing fiber and 40% by weight of cotton were mixed.

The LOI values of the composite fibers obtained in Example 1 and Comparative Example 1 were measured. Table 1 shows the results.

[0023]

[Table 1]

As is clear from Table 1, the halogen-containing fiber containing the zinc stannate compound according to the present invention has been conventionally used.
It is possible to obtain even higher flame retardancy than halogen-containing fibers containing antimony trioxide, which was considered to be most flame-retardant by mixing other combustible fibers.

Example 2 A copolymer consisting of 51.0% by weight of acrylonitrile and 49.0% by weight of vinylidene chloride was added to dimethylformaldehyde at a resin concentration of 30% by weight.
It dissolved so that it might become. To the obtained resin solution, zinc hydroxystannate was added so as to be 40% by weight with respect to the copolymer to prepare a spinning dope. This spinning dope was used at 20 ° C. using a nozzle having a nozzle hole diameter of 0.08 mm and 300 holes.
Extruded in 55% aqueous dimethylformamide,
Pulled up at a speed of 2.5 m / min, washed with water and then 130 ° C
For 8 minutes, and then stretched 3 times at 140 ° C., and further heat-treated at 145 ° C. for 5 minutes,
A halogen-containing fiber having a denier of 2 denier was obtained. 40% by weight of this halogen-containing fiber and 60% by weight of cotton were blended.

(Comparative Example 2) The same as Example 2 except that antimony trioxide was added in an amount of 40% by weight to the copolymer of Example 2 instead of 40% by weight of zinc hydroxystannate. A halogen-containing fiber added with antimony trioxide was obtained by the method. 40% by weight of the halogen-containing fiber and 6% of cotton
0% by weight was mixed.

The LOI values of the composite fibers obtained in Example 2 and Comparative Example 2 were measured. Table 2 shows the results.

[0028]

[Table 2]

As is clear from Table 2, in the case of the halogen-containing fiber containing zinc hydroxystannate, the halogen-containing fiber containing antimony trioxide is higher than the halogen-containing fiber containing antimony trioxide even if the mixing ratio of the other combustible fibers is increased. Higher flame retardancy can be obtained.

[0030]

The halogen-containing fiber containing the zinc stannate compound according to the present invention, and the fiber composite using the same,
It is possible to obtain a composite flame-retardant fiber having a higher flame retardancy than when a conventional antimony compound is used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location D03D 15/12 D03D 15/12 Z

Claims (3)

[Claims] 1. A polymer containing 17 to 70% by weight of a halogen, wherein a zinc stannate compound is added to the polymer in an amount of 20 to 50% by weight.
Halogen-containing fiber contained by weight. 2. The method of claim 1, wherein the halogen-containing polymer comprises 30 to 70 parts by weight of acrylonitrile, a halogen-containing vinyl monomer and / or a halogen-containing vinylidene monomer.
The halogen-containing fiber according to claim 1, comprising from 30 to 30 parts by weight, and from 0 to 10 parts by weight of a vinyl monomer copolymerizable therewith. 3. A polymer containing 17 to 70% by weight of a halogen, and a zinc stannate compound in an amount of 20 to 50% based on the polymer.
85 to 15% by weight of halogen-containing fibers
And fibers 15 composed of natural fibers and / or chemical fibers
A flame-retardant fiber composite in which the composite is made up to about 85% by weight.